CN102608180B - Bioelectrochemical sensor for detecting silver ion and preparation method thereof - Google Patents
Bioelectrochemical sensor for detecting silver ion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a bioelectrochemical sensor for detecting a silver ion and a preparation method thereof. The sensor is a three-electrode system sensor, wherein a counter electrode is a platinum electrode, a reference electrode is a saturated calomel electrode, and a working electrode is a gold electrode. The sensor is characterized in that: a template DNA (Desoxvribose Nucleic Acid) is modified on the gold electrode and has the sequence of 5'-CCTACGACTGGATGACGATCCCTACGACTGAAAAAAAAAAAA-C6-SH-3'. According to the bioelectrochemical sensor, the characteristic that the silver ion has strong affinity to cytosine is utilized, and the advantages of sensitivity and convenience of electrochemical detection are combined, so that the silver ion is detected ingeniously, a linear range is within 10pM-100nM, and the detection limit is about 3.3pM.
Description
Technical field
The present invention relates to a kind of new bio electrochemical sensor and preparation method thereof, particularly a kind of bioelectrochemical sensor that detects silver ion and preparation method thereof.
Technical background
Silver, as a kind of very important transition metal, is widely used in various fields, and for example cosmetics, jewelry, currency, as catalyzer and conductor etc.Silver ion has certain toxic action for some bacterium, virus, algae, and its principle is that silver ion can suppress the activity that contains free sulfhydryl groups proteinase, thereby suppresses its biological function.As the trace element of Body composition, a small amount of silver ion is harmless to people, but along with silver being widely used in industry, the discharge of silver ion waste liquid is day by day serious for the pollution of water source and soil, increasing silver ion is enriched in human body, and human body is worked the mischief.WHO specifies that silver ion is below 0.05 ppm to the safety value of human body, and the safety value in potable water is 0.05 mg/L, as can be seen here, is very important for the accurate detection of silver ion.The technology that detects now silver ion mainly comprises inductively coupled plasma technology, atomic absorption spectrography (AAS) and stripping voltammetry, the above two have very high requirement for instrument and equipment and operator, thereby the latter usually needs the participation of mercury ion to produce new pollution in the time detecting, therefore, invent a kind of simple, safe Silver detection method and seem very urgent.
Electrochemica biological sensor be a class using electrode as signal converter, the biology sensor of being measured with current potential or electric current, is mainly constituted by biomolecule identification and information converting member two parts.Electrochemical system is realized inputing or outputing of electric energy by electrode, thereby obtains the electric signal of electrode face finish material, and conventional is three-electrode system.Three-electrode system comprises working electrode, auxiliary electrode (also claiming electrode) and contrast electrode, wherein be platinum electrode to electrode, contrast electrode is saturated calomel electrode, working electrode is gold electrode, flow through working electrode and to electrode of electric current.The measured current potential of working electrode is for contrast electrode.Electrochemical method, as an alanysis detection method, has the advantages such as equipment is cheap, highly sensitive, simple and efficient.Wherein, timing coulometry is very high because of its sensitivity, is often used as quantitative detection.
Summary of the invention
One of object of the present invention is to provide a kind of bioelectrochemical sensor that detects silver ion.
Two of object of the present invention is to provide the preparation method of this sensor.
For achieving the above object, the present invention adopts following mechanism: the DNA base pairing that metal participates in has attracted people more and more to pay close attention to owing to can changing the conformation of DNA.Research discovery, silver ion tendency is combined with the DNA of cytimidine mispairing, forms cytimidine-silver ion-cytimidine structure, thereby increases widely the stability of mismatched dna.The present invention designs the template DNA chain that one section of 3 ' end contains sulfydryl, comprise above two sections similar and with the not exclusively complementary repetitive sequence of primed DNA and the restriction enzyme site of an endonuclease BasBI, this template DNA chain can be fixed on gold electrode by the sulfydryl of 3 ' end; Design in addition a free primed DNA chain, only have a cytimidine mispairing not exclusively complementary with template DNA chain.In the time containing silver ion in system, article two, DNA chain can form cytimidine-silver ion-cytimidine nucleic acid metal composite, now template DNA chain and primed DNA chain form stable duplex structure, identified by Bst nucleic acid polymerase, thereby start to copy, taking template DNA chain as template, utilize the dNTP in system, primed DNA chain is constantly extended and lengthened to 3 ' end from 5 ' end.After primed DNA extends completely, Bst nucleic acid polymerase comes off from two strands, and the restriction enzyme site coming out is identified by endonuclease BsaBI, two chains of cutting double-stranded DNA, and result, double-stranded DNA is cut to two parts, forms two new primed DNAs.New primed DNA, under the effect of silver ion, is combined with template DNA, restarts new round reaction, until template DNA is cut complete.Whole course of reaction can electricity consumption chemical signal molecule six ammino ruthenium [Ru (NH
3)
6]
3+characterize [Ru (NH
3)
6]
3+because electrostatic interaction can be adsorbed on the phosphoric acid skeleton of DNA, therefore, [Ru (NH
3)
6]
3+the height of electrochemical signals can quantitative reaction be fixed on gold electrode surfaces DNA number, thereby the height of reaction concentration of silver ions.Specifically, initial, template DNA is fixed on gold electrode surfaces, and now template DNA is complete, a large amount of [Ru (NH
3)
6]
3+be adsorbed on template DNA, thereby produce very high electrochemical signals; When there being silver ion to exist, in system, there is the circular response of above-mentioned extension and cutting, template DNA is cut to be shortened, [Ru (NH
3)
6]
3+the electrochemical signals producing is corresponding diminishing also, the number changing by electrochemical signals, and we can calculate the number of silver ion.
According to above-mentioned mechanism, the present invention adopts following technical scheme:
A kind of bioelectrochemical sensor that detects silver ion, for three-electrode system sensor, wherein platinum electrode to electrode, contrast electrode is saturated calomel electrode, working electrode is gold electrode, it is characterized in that being modified with template DNA on described gold electrode, this gold electrode that is modified with template DNA is carried out to enzyme and cut processing, reaction buffer solution used contains 100 nM primed DNAs, 0.5 U/ μ L BsaBI endonuclease, 0.05 U/ μ L Bst nucleic acid polymerase, 50 μ M dNTPs, 1 × NE buffering 4; Described 1 × NE buffering 4 is: 50 mM KAc, the Tris-HAc of 20 mMpH 7.9,10 mM Mg (Ac)
2, described primed DNA sequence is: 5 '-CAGTCCTAGG-3 '; Cut with enzyme the gold electrode of processing and carry out electrochemical measurement, Electrochemical Detection damping fluid used is for containing 50 μ M [Ru (NH
3)
6]
3+10 mM Tris-HCl, the detection damping fluid of pH=7.4; The sequence of described template DNA is: 5 '-CCTA CGACTGGATGACGATCCCTACGACTGAAAAAAAAAAAA-C
6-SH-3 ', the modification density of this template DNA on gold electrode is: 1.2 × 10
12individual molecule/square centimeter～1.2 × 10
13individual molecule/square centimeter.This sequence is to design for the effect of silver ion and base.Design concept is easily combined with cytimidine according to silver ion, makes two dissociative DNA strands with a cytimidine mispairing can form stable duplex structure in the situation that having silver ion to exist.Now stable two strands can be identified by DNA nucleic acid polymerase, causes double-stranded expansion extension, by endonuclease identification cutting, forms two DNA fragmentations afterwards.Article one, DNA fragmentation is primed DNA, and another be new produce can with the DNA fragmentation of template DNA complementary pairing, thereby carry out the cutting of a new round, cause the reduction of electrochemical signals.The sequence of the DNA designing can directly give nucleic acid synthetic company.The modification density of template DNA on gold electrode is 1.2 × 10
12individual molecule/square centimeter～1.2 × 10
13between individual molecule/square centimeter.
Prepare a method for the biology sensor of above-mentioned detection silver ion, it is characterized in that the concrete steps of the working electrode of preparing this sensor are:
A. the gold electrode of processing is placed in to 0.5 M H
2sO
4in, in 0～1.55 V voltage range, carry out cyclic voltammetry scan, sweep speed and be set to 100 mV/s, until reach stable;
B. dry up after step a gained gold electrode with nitrogen, this gold electrode is immersed in and contains the template DNA chain that concentration is 1 μ M, the TCEP of Tris-HCl, 10 mM and the NaCl of 0.1 M of 10 mM, the pH of solution is in 7.4 buffer solution, be inverted after 15～18 hours, be immersed in again in 1 mM sulfydryl hexanol aqueous solution and react 0.5～1.5 hour, rinse with ultrapure water, and dry up with nitrogen, obtain the gold electrode that template DNA chain is modified.
The concrete steps of the disposal route of above-mentioned gold electrode are: drip 20 μ L Piranha solution in pending gold electrode surfaces, i.e. and the concentrated sulphuric acid: the volume ratio of hydrogen peroxide is 3:1, reaction 2 min, rinse well with ultrapure water, and nitrogen dries up; Gold electrode is polished on 5000 order sand paper after 5 min, on the silk of mortar that contains granularity and be respectively the aluminium oxide of 1 μ m, 0.3 μ m, 0.05 μ m, be polished to successively minute surface, then ultrasonic 5 min successively in ethanol, ultrapure water, remove impurity.
Detect a method for silver ion, adopt the biology sensor of above-mentioned detection silver ion, it is characterized in that the concrete steps of the method are:
A. the working electrode gold electrode in biology sensor is immersed in to reaction buffer solution and solution to be measured by the mixed liquor of the volume ratio formation of 9:1; Described reaction buffer solution contains 100 nM primed DNAs, 0.5 U/ μ L BsaBI endonuclease, 0.05 U/ μ L Bst nucleic acid polymerase, 50 μ M dNTPs, 1 × NE buffering 4; Described is: 50 mM KAc, the Tris-HAc of 20 mMpH 7.9,10 mM Mg (Ac)
2, 55～65 degree reaction 5～10 minutes, rinse with ultrapure water, dry up with nitrogen, obtain enzyme and cut the gold electrode of processing; Described primed DNA sequence is: 5 '-CAGTCCTAGG-3 ';
B. under inert atmosphere, the gold electrode of step a gained is put into Electrochemical Detection damping fluid, described Electrochemical Detection damping fluid is for containing 50 μ M [Ru (NH
3)
6]
3+10 mM Tris-HCl, the detection damping fluid of pH=7.4, adopts cyclic voltammetry or timing coulometry to carry out Electrochemical Scanning, reaction buffering is for adding 50 μ M [Ru (NH
3)
6]
3+10 mM pH 7.4 Tris-HCl; Sweep speed while adopting cyclic voltammetry is 50 mV/s, and sweep limit is-0.45 V～0.05 V; Recurrence interval while adopting timing coulometry is 250 ms, and initial potential 0.2 V stops current potential-0.5 V.
The present invention has built a kind of bioelectrochemical sensor that detects silver ion, utilize the feature that silver ion and cytimidine affinity are strong, together with nucleic acid polymerase priming reaction that silver ion is caused is sensitive with Electrochemical Detection, advantage is combined and is used in easily, by the exponential type template DNA of degrading, silver ion is carried out to very sensitive detection.For some other metal that has stronger adhesion with base and can stablize double-stranded DNA structure, for example mercury ion, also can detect in theory by this method, is with a wide range of applications.
Brief description of the drawings
Fig. 1 is at 10 mM Tris-HCl (pH 7.4) and 50 μ M [Ru (NH
3)
6]
3+in solution, the gold electrode that template DNA is modified and under without silver ion existence condition and have under silver ion existence condition through polymeric enzyme reaction and endonuclease reaction cyclic voltammogram after treatment.
Fig. 2 is at 10 mM Tris-HCl (pH 7.4) and 50 μ M [Ru (NH
3)
6]
3+in solution, the gold electrode that template DNA is modified detects the timing electric quantity curve of variable concentrations silver ion (being respectively 0 M, 50 pM, 100 pM, 500 pM, 1 nM, 10 nM, 50 nM, 100 nM, 250 nM, 500 nM and 1 μ M from a to k).
Fig. 3 is the relation curve of different concentration of silver ions (0 M, 50 pM, 100 pM, 500 pM, 1 nM, 10 nM, 50 nM, 100 nM, 250 nM, 500 nM and 1 μ M) and electric weight difference.Wherein to insert figure be concentration of silver ions at 10 pM to the logarithm value within the scope of 100 nM and the relation curve between electric weight difference.
Fig. 4 exists respectively in the situation of 1 μ M silver ion and 1 other metallic ions of μ M, after polymeric enzyme reaction and endonuclease reaction processing, at 10 mM Tris-HCl (pH 7.4) and 50 μ M [Ru (NH
3)
6]
3+in solution, the gold electrode that template DNA is modified detects the surface electrical spirogram obtaining through timing coulometry.
Embodiment
Embodiment mono-: the gold electrode preparation that template DNA is modified
Drip 20 μ L Piranha solution (concentrated sulphuric acid: hydrogen peroxide=3:1) reaction 2 min in pending gold electrode surfaces, rinse well with ultrapure water, nitrogen dries up.Gold electrode is polished on 5000 order sand paper after 5 min, respectively contain aluminium oxide (granularity is respectively 1 μ m, 0.3 μ m, 0.05 μ m) is polished to minute surface on the silk of mortar successively, then ultrasonic 5 min successively in ethanol, ultrapure water, remove impurity.The gold electrode of handling well is placed on to 0.5 M H
2sO
4middle cyclic voltammetry scan.Scanning voltage scope 0～1.55 V is set, sweep velocity 100 mV/s, setting 20 circles, to be swept to cyclic voltammetry curve stable, dries up with nitrogen, obtains the clean naked gold electrode of surface treatment, can be used for the modification of sulfydryl DNA.This gold electrode is immersed in to 1 μ M template DNA solution (10 mM Tris-HCl, 10 mM TCEP, and 0.1 M NaCl (pH 7.4)) be inverted and spend the night 16 hours, be immersed in again in 1 mM sulfydryl hexanol solution and react 1 hour, rinse well with ultrapure water, nitrogen dries up, and obtains the gold electrode that template DNA is modified.
Embodiment bis-: the flow process that detects silver ion
The gold electrode that template DNA is modified is put into and is contained 100 nM primed DNAs, 0.5 U/ μ L BsaBI endonuclease, 0.05 U/ μ L Bst nucleic acid polymerase, 50 μ M dNTPs, 1 × NE cushions 4 (50 mM KAc, 20 mM Tris-HAc (pH 7.9), 10 mM Mg (Ac)
2) silver ion reactant liquor to be measured in 60 degree reaction 7 minutes, rinse with ultrapure water afterwards, dry up with nitrogen, obtain enzyme and cut the gold electrode of processing, put into Electrochemical Detection damping fluid, carry out Electrochemical Scanning.Associated nucleic acid sequences is as follows:
The sequence of template DNA is: 5 '-CCTACGACTGGATGACGATCCCTACGACTGAAA A AA AAAAAA-C
6-SH-3 '
Primed DNA sequence is: 5 '-CAGTCCTAGG-3 '
Electrochemical Detection correlation parameter and damping fluid: in cyclic voltammetric and the experiment of timing electric weight, reaction solution is for containing 50 μ M [Ru (NH
3)
6]
3+10 mM Tris-HCl (pH 7.4), wherein cyclic voltammetry scan speed is 50 mV/s, sweep limit is-0.45 V～0.05 V.For the experiment of timing electric weight, the recurrence interval is 250 ms, and initial potential 0.2 V stops current potential-0.5 V.First logical nitrogen 15 min in damping fluid of all above-mentioned experiments, detect after removing the oxygen in solution.
As shown in Figure 1, when not having in solution in the situation of silver ion, add the primed DNA cyclic voltammetry curve of gained and result of template DNA itself after enzyme is processed to be more or less the same, illustrate when thering is no silver ion, due to double-stranded DNA unstable, primed DNA is not hybridized with template DNA, and nucleic acid polymerase and endonuclease do not act on template DNA, therefore electrochemical signals molecule [Ru (NH
3)
6]
3+still Electrostatic Absorption is on phosphatase nucleic acid skeleton in large quantities, and electrochemical signals does not have significant change.But, in the time containing 1 μ M silver ion in system, silver ion and cytimidine form the metal base base complex of cytimidine-silver ion-cytimidine, greatly increase the stability that template DNA and primed DNA hybridization produce double-stranded DNA, so nucleic acid polymerase and endonuclease performance biological function, template DNA is constantly cut, becomes shorter and shorter at the template DNA of electrode surface, is now attached to the [Ru (NH in nucleic acid backbone
3)
6]
3+also corresponding tailing off, the electrochemical signals obtaining also obviously diminishes.
Embodiment tri-: the detection of variable concentrations silver ion
The gold electrode of having modified template DNA is immersed in variable concentrations silver ion (0 M, 50 pM, 100 pM, 500 pM, 1 nM, 10 nM, 50 nM, 100 nM, 250 nM, 500 nM and 1 μ M) reactant liquor, after two enzyme reactions, put into detection damping fluid and adopt timing coulometry to carry out Electrochemical Detection.
As shown in Figure 2, along with the increase of concentration of silver ions, the electrochemical signals that timing coulometry obtains diminishes gradually, and this is because silver ion is more, and template DNA cut in same time is also just more, so electrochemical signals is less.
Variation (reducing) value of concentration of silver ions and timing electric weight is mapped and obtain Fig. 3.In addition, the insertion figure demonstration of Fig. 3, in the time that concentration of silver ions changes between 10 pM～100 nM, the difference of the logarithm value of concentration of silver ions and timing electric weight presents good linear relationship, can be used as the foundation that silver ion quantitatively detects.It is 3 that the minimum detectability of silver ion is about 3.3 pM(signal to noise ratio (S/N ratio)s).
Embodiment tetra-: bioelectrochemical sensor specificity research
In order to verify the specificity of this bioelectrochemical sensor, we are with other metals (Na
+, Zn
2+, Fe
2+, Pb
2+, Al
3+, Cr
6+) in contrast, according to above-mentioned experimental technique, the gold electrode that template DNA is modified is immersed in and in the detection liquid of same isoconcentration different metal, carries out two enzyme reaction 7 min, then puts into Electrochemical Detection liquid timing coulometry and detect.As shown in Figure 4, in the time containing 1 μ M silver ion in solution, the electrochemical signals minimum of gained, be about 1.72 μ C, and electrochemical signals is all larger when other metals, close during with silver ion not, illustrate that this bioelectrochemical sensor has very high selectivity and specificity for silver ion.
Above result shows, this biology sensor has good selectivity and specificity for silver ion, convenient experimental operation, and testing result is sensitive.Same principle can be generalized to other and base has in the metal detection of stronger combination, and application prospect is extensive.
sequence table
<110> Shanghai University
<120> detects bioelectrochemical sensor of silver ion and preparation method thereof
<160> 2
<210> 1
<211> 42
<212> PRT
<213> artificial sequence
<400> 1
CCTAC GACTG GATGA CGATC CCTAC GACTG AAA A A A AAA A AA-C
6-SH 42 。
<210> 2
<211> 10
<212> PRT
<213> artificial sequence
<400> 1
CAGTC CTAGG 10
Claims (3)
1. one kind is detected the bioelectrochemical sensor of silver ion, for three-electrode system sensor, wherein platinum electrode to electrode, contrast electrode is saturated calomel electrode, working electrode is gold electrode, it is characterized in that being modified with template DNA on described gold electrode, to this gold electrode that is modified with template DNA carry out enzyme cut process reaction buffer solution used contain 100 nM primed DNAs, 0.5 U/ μ L BsaBI endonuclease, 0.05 U/ μ L Bst nucleic acid polymerase, 50 μ M dNTPs, 1 × NE buffering 4; 1 described × NE cushions 4 by 50 mM KAc, the Tris-HAc of 20 mM pH 7.9, and 10 mM Mg (Ac)
2composition; Described primed DNA sequence is: 5 '-CAGTCCTAGG-3 '; Cut Electrochemical Detection damping fluid that the gold electrode of processing carries out electro-chemical investigating as containing 50 μ M [Ru (NH taking enzyme
3)
6]
3+10 mM Tris-HCl, the detection damping fluid of pH=7.4; The sequence of described template DNA is: 5 '-CCTA CGACTGGATGACGATCCCTACGACTGAAAAAAAAAAAA-C
6-SH-3 ', the modification density of this template DNA on gold electrode is: 1.2 × 10
12individual molecule/square centimeter～1.2 × 10
13individual molecule/square centimeter.
2. prepare a method for the bioelectrochemical sensor of detection silver ion according to claim 1, it is characterized in that the concrete steps of the working electrode of preparing this sensor are:
A. the gold electrode of processing is placed in to 0.5 M H
2sO
4in, in 0～1.55 V voltage range, carry out cyclic voltammetry scan, sweep speed and be set to 100 mV/s, until reach stable; The concrete steps of the disposal route of described gold electrode are: drip 20 μ L Piranha solution in pending gold electrode surfaces, i.e. and the concentrated sulphuric acid: the volume ratio of hydrogen peroxide is 3:1, reaction 2 min, rinse well with ultrapure water, and nitrogen dries up; Gold electrode is polished on 5000 order sand paper after 5 min, on the silk of mortar that contains granularity and be respectively the aluminium oxide of 1 μ m, 0.3 μ m, 0.05 μ m, be polished to successively minute surface, then ultrasonic 5 min successively in ethanol, ultrapure water, remove impurity;
B. dry up after step a gained gold electrode with nitrogen, this gold electrode is immersed in and contains the template DNA that concentration is 1 μ M, the TCEP of Tris-HCl, 10 mM and the NaCl of 0.1 M of 10 mM, the pH of solution is in 7.4 buffer solution, be inverted after 15～18 hours, be immersed in again in 1 mM sulfydryl hexanol aqueous solution and react 0.5～1.5 hour, rinse with ultrapure water, and dry up with nitrogen, obtain the gold electrode that template DNA is modified.
3. detect a method for silver ion, adopt the bioelectrochemical sensor of detection silver ion according to claim 1, it is characterized in that the concrete steps of the method are:
A. the working electrode gold electrode in biology sensor is immersed in to described reaction buffer solution and solution to be measured by the mixed liquor of the volume ratio formation of 9:1; 55～65 degree reaction 5～10 minutes, rinse with ultrapure water, dry up with nitrogen, obtain enzyme and cut the gold electrode of processing;
B. under inert atmosphere, the gold electrode of step a gained is put into described Electrochemical Detection damping fluid, adopt cyclic voltammetry or timing coulometry to carry out Electrochemical Scanning, the sweep speed while adopting cyclic voltammetry is 50 mV/s, and sweep limit is-0.45 V～0.05 V; Recurrence interval while adopting timing coulometry is 250 ms, and initial potential 0.2 V stops current potential-0.5 V.
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| CN104713924B (en) * | 2014-10-27 | 2017-06-20 | 北京航空航天大学 | A kind of aluminium oxide nano channel thin film and preparation method thereof, application process |
| CN105445349A (en) * | 2015-10-14 | 2016-03-30 | 上海大学 | Gold electrode decorated by specific polypeptide probe as well as preparation method and application thereof |
| CN105911289B (en) * | 2016-04-13 | 2018-04-10 | 南京大学 | A kind of electrochemical sensor and its preparation and application based on dynamic sandwich structure |
| CN107677661A (en) * | 2017-08-16 | 2018-02-09 | 樊之雄 | A kind of detection method of the chemiluminescence sensor based on adaptation body measurement silver ion |
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